EP0821011A3 - Process for the preparation of ethylene-based polymers and catalyst system used therein - Google Patents

Process for the preparation of ethylene-based polymers and catalyst system used therein Download PDF

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Publication number
EP0821011A3
EP0821011A3 EP97118519A EP97118519A EP0821011A3 EP 0821011 A3 EP0821011 A3 EP 0821011A3 EP 97118519 A EP97118519 A EP 97118519A EP 97118519 A EP97118519 A EP 97118519A EP 0821011 A3 EP0821011 A3 EP 0821011A3
Authority
EP
European Patent Office
Prior art keywords
ethylene
preparation
metallocene compound
racemic
catalyst system
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP97118519A
Other languages
German (de)
French (fr)
Other versions
EP0821011A2 (en
EP0821011B1 (en
Inventor
Tiziano Dall'occo
Luigi Resconi
Guilio Balbontin
Enrico Albizzati
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Basell Polyolefine GmbH
Original Assignee
Montell Technology Co BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=11369136&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0821011(A3) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Montell Technology Co BV filed Critical Montell Technology Co BV
Publication of EP0821011A2 publication Critical patent/EP0821011A2/en
Publication of EP0821011A3 publication Critical patent/EP0821011A3/en
Application granted granted Critical
Publication of EP0821011B1 publication Critical patent/EP0821011B1/en
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61912—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61916—Component covered by group C08F4/60 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/6192—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/61922—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/61927—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

A process for the preparation of ethylene polymers is disclosed, comprising the polymerization reaction of ethylene in the presence of a catalyst consisting of the reaction product of:
  • (A) a mixture of the racemic and meso isomers of a stereorigid metallocene compound of a transition metal, belonging to Groups III, IV or V or the lanthanides in the Periodic Table of the Elements, with two cyclopentadienyl ligands connected to each other by a chemical bridge, and
  • (B) at least one co-catalyst capable of activating both the racemic form and the meso form of the metallocene compound, selected from the alumoxanes and the compounds capable of forming an alkylmetallocene cation.
    • In particular the process is suitable to prepare ethylene copolymers with uniform distribution of the comonomer along the polymer chain and broad molecular weight distribution.
    EP97118519A 1994-06-20 1995-06-19 Process for the preparation of ethylene-based polymers Revoked EP0821011B1 (en)

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    ITMI941279 1994-06-20
    ITMI941279A IT1270253B (en) 1994-06-20 1994-06-20 ETHYLENE COPOLYMERS AND PROCEDURE FOR THE PREPARATION OF ETHYLENE POLYMERS
    EP95924286A EP0742799B1 (en) 1994-06-20 1995-06-19 Ethylene copolymers

    Related Parent Applications (1)

    Application Number Title Priority Date Filing Date
    EP95924286A Division EP0742799B1 (en) 1994-06-20 1995-06-19 Ethylene copolymers

    Publications (3)

    Publication Number Publication Date
    EP0821011A2 EP0821011A2 (en) 1998-01-28
    EP0821011A3 true EP0821011A3 (en) 1998-05-06
    EP0821011B1 EP0821011B1 (en) 2001-01-31

    Family

    ID=11369136

    Family Applications (2)

    Application Number Title Priority Date Filing Date
    EP95924286A Revoked EP0742799B1 (en) 1994-06-20 1995-06-19 Ethylene copolymers
    EP97118519A Revoked EP0821011B1 (en) 1994-06-20 1995-06-19 Process for the preparation of ethylene-based polymers

    Family Applications Before (1)

    Application Number Title Priority Date Filing Date
    EP95924286A Revoked EP0742799B1 (en) 1994-06-20 1995-06-19 Ethylene copolymers

    Country Status (25)

    Country Link
    US (2) US6136936A (en)
    EP (2) EP0742799B1 (en)
    JP (2) JP3698437B2 (en)
    KR (1) KR100379138B1 (en)
    CN (1) CN1092672C (en)
    AT (2) ATE199018T1 (en)
    AU (1) AU689915B2 (en)
    BG (1) BG100411A (en)
    BR (1) BR9506041A (en)
    CA (1) CA2169841A1 (en)
    CZ (1) CZ290960B6 (en)
    DE (2) DE69520051T2 (en)
    ES (2) ES2121402T3 (en)
    FI (1) FI960741A (en)
    IL (1) IL114196A (en)
    IT (1) IT1270253B (en)
    MX (1) MX9600690A (en)
    MY (1) MY117891A (en)
    NO (1) NO960650L (en)
    NZ (1) NZ289111A (en)
    PL (1) PL182374B1 (en)
    RU (1) RU2155776C2 (en)
    SK (1) SK281515B6 (en)
    WO (1) WO1995035333A2 (en)
    ZA (1) ZA955102B (en)

    Families Citing this family (28)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    IT1272922B (en) * 1995-01-23 1997-07-01 Spherilene Srl PROCEDURE FOR THE PREPARATION OF METALLOCENIC COMPOUNDS
    JP3071145B2 (en) * 1995-05-16 2000-07-31 ユニベーション・テクノロジーズ・エルエルシー Production of polyethylene using stereoisomeric metallocene
    UA47394C2 (en) * 1995-05-16 2002-07-15 Юнівейшн Текнолоджіз, Ллс Ethylene polymer with improved processability and an article containing the ethylene polymer
    DE69720609T2 (en) * 1996-07-16 2003-11-13 Basell Polyolefine Gmbh Process for modifying the Rac / Meso ratio of a metallocene compound
    DE69813958T2 (en) * 1997-07-18 2004-03-11 Mitsui Chemicals, Inc. Unsaturated copolymers, process for their preparation and mixtures containing them
    DE69907785T2 (en) 1998-03-09 2004-02-12 Basell Poliolefine Italia S.P.A. Multi-stage process for olefin polymerization
    US6177527B1 (en) 1998-09-08 2001-01-23 Union Carbide Chemical & Plastics Technology Corporation Process for the preparation of polyethylene or polypropylene
    CN1293677A (en) 1998-11-20 2001-05-02 蒙特尔技术有限公司 Bridged metallocenes preparation, use in catalytic system
    KR20010113933A (en) * 1999-05-14 2001-12-28 진 엠.보스 Highly Crystalline EAODM Interpolymers
    SG97919A1 (en) † 1999-08-31 2003-08-20 Sumitomo Chemical Co Ethylene-alpha-olefin copolymer and polyethylene composition
    SG96700A1 (en) * 2001-09-27 2003-06-16 Sumitomo Chemical Co Catalyst component for addition polymerization, process for producing catalyst for addition polymerization and process for producing addition polymer
    DE10244212A1 (en) * 2002-09-23 2004-03-25 Bayer Aktiengesellschaft Water- and halogen free dispersion, useful for the production of transparent UV-protective coatings, comprises redispersable primary particle zinc oxide particles having a diameter of 1-200 nm and aminoalcohols
    AU2003282957A1 (en) * 2002-11-07 2004-06-03 Dow Global Technologies, Inc. Process for homo- or copolymerization of conjugated dienes and in situ formation of polymer blends and products made thereby
    CA2650826A1 (en) * 2006-06-27 2007-08-01 Univation Technologies, Llc Improved polymerization processes using metallocene catalysts, their polymer products and end uses
    ATE503781T1 (en) * 2006-07-25 2011-04-15 Mitsui Chemicals Inc ETHYLENE POLYMER PARTICLES, PRODUCTION METHOD THEREOF AND MOLDED BODY USING THEREOF
    EP2275201A1 (en) * 2009-06-18 2011-01-19 Total Petrochemicals Research Feluy Polymerization process with improved polymer homogeneity
    US20110003940A1 (en) * 2009-07-01 2011-01-06 Dow Global Technologies Inc. Ethylene-based polymer compositions for use as a blend component in shrinkage film applications
    JP5767202B2 (en) * 2012-12-18 2015-08-19 旭化成ケミカルズ株式会社 Ethylene polymer, stretched molded body, microporous membrane, and battery separator
    JP5767203B2 (en) * 2012-12-19 2015-08-19 旭化成ケミカルズ株式会社 Ethylene polymer, stretched molded body, microporous membrane, and battery separator
    KR101689456B1 (en) * 2015-01-23 2016-12-23 한화토탈 주식회사 Ethylene-Olefin Copolymer and preparation thereof
    FR3045613B1 (en) * 2015-12-17 2017-12-15 Michelin & Cie COPOLYMER OF ETHYLENE AND BUTADIENE OF HOMOGENEOUS MICROSTRUCTURE
    FR3045612B1 (en) * 2015-12-17 2017-12-15 Michelin & Cie COPOLYMER OF ETHYLENE AND BUTADIENE OF HOMOGENEOUS MICROSTRUCTURE
    US10882925B2 (en) 2017-11-29 2021-01-05 Exxonmobil Chemical Patents Inc. Catalysts that produce polyethylene with broad, bimodal molecular weight distribution
    US10889663B2 (en) 2017-11-29 2021-01-12 Exxonmobil Chemical Patents Inc. Asymmetric ANSA-metallocene catalyst compounds for producing polyolefins having a broad molecular weight distribution
    KR102258230B1 (en) * 2018-10-19 2021-05-28 한화솔루션 주식회사 Polyolefin
    US11014997B2 (en) 2019-05-16 2021-05-25 Chevron Phillips Chemical Company Lp Dual catalyst system for producing high density polyethylenes with long chain branching
    US11267919B2 (en) 2020-06-11 2022-03-08 Chevron Phillips Chemical Company Lp Dual catalyst system for producing polyethylene with long chain branching for blow molding applications
    CN114591455B (en) * 2020-12-03 2023-10-31 中国石油天然气股份有限公司 Catalyst, preparation method thereof and olefin polymerization catalyst system

    Citations (1)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    EP0584609A2 (en) * 1992-08-15 1994-03-02 Hoechst Aktiengesellschaft Process for preparing polyolefins

    Family Cites Families (37)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US4530914A (en) * 1983-06-06 1985-07-23 Exxon Research & Engineering Co. Process and catalyst for producing polyethylene having a broad molecular weight distribution
    US4701432A (en) * 1985-11-15 1987-10-20 Exxon Chemical Patents Inc. Supported polymerization catalyst
    US5084534A (en) 1987-06-04 1992-01-28 Exxon Chemical Patents, Inc. High pressure, high temperature polymerization of ethylene
    US5229022A (en) 1988-08-01 1993-07-20 Exxon Chemical Patents Inc. Ethylene alpha-olefin polymer substituted mono- and dicarboxylic acid dispersant additives (PT-920)
    DE3836059A1 (en) * 1988-10-22 1990-05-03 Hoechst Ag METHOD FOR PRODUCING AN ETHYLENE PROPYLENE COPOLYMER
    US5218071A (en) * 1988-12-26 1993-06-08 Mitsui Petrochemical Industries, Ltd. Ethylene random copolymers
    DE3916555A1 (en) 1989-05-20 1990-11-22 Hoechst Ag PROCESS FOR THE PRODUCTION OF ETHYLENE POLYMERS
    JP2769728B2 (en) * 1989-10-31 1998-06-25 日本石油化学株式会社 Measurement method of branch distribution of polymer
    TW198726B (en) * 1989-12-29 1993-01-21 Mitsui Petroleum Chemicals Ind
    US5145818A (en) * 1989-12-29 1992-09-08 Mitsui Petrochemical Industries, Ltd. Olefin polymerization catalyst and process for the polymerization of olefins
    TW206240B (en) * 1990-02-13 1993-05-21 Mitsui Petroleum Chemicals Ind
    KR0123370B1 (en) * 1990-06-22 1997-11-12 벤 씨, 카덴헤드 Aluminum-free monocyclopentadienyl metallocene catalysts for olefin polymerization
    ES2071888T3 (en) * 1990-11-12 1995-07-01 Hoechst Ag BISINDENILMETALOCENOS SUBSTITUTED IN POSITION 2, PROCEDURE FOR ITS PREPARATION AND USE AS CATALYSTS IN THE POLYMERIZATION OF OLEFINS.
    US5631335A (en) 1991-05-09 1997-05-20 Phillips Petroleum Company Process of polymerizing olefins using diphenylsilyl or dimethyl tin bridged 1-methyl fluorenyl metallocenes
    ATE136040T1 (en) * 1991-05-27 1996-04-15 Hoechst Ag METHOD FOR PRODUCING POLYOLEFINS WITH BROAD MOLAR MASS DISTRIBUTION
    CA2069995C (en) * 1991-05-31 1996-04-09 Mitsui Chemicals, Incorporated Olefin polymerization solid catalyst, olefin polymerization catalyst and olefin polymerization
    AU660043B2 (en) * 1991-07-18 1995-06-08 Exxon Chemical Patents Inc. Heat sealed article
    TW300901B (en) * 1991-08-26 1997-03-21 Hoechst Ag
    EP0537686B1 (en) * 1991-10-15 2005-01-12 Basell Polyolefine GmbH Process for preparing an olefinpolymer by using metallocenes having specially substituted indenylligands
    DE69231975T2 (en) * 1991-11-07 2002-04-18 Exxonmobil Chem Patents Inc METHOD FOR PRODUCING POLYOLEFINES
    TW318184B (en) * 1991-11-30 1997-10-21 Hoechst Ag
    WO1993012151A1 (en) * 1991-12-13 1993-06-24 Exxon Chemical Patents Inc. Ethylene/longer alpha-olefin copolymers
    JPH05310847A (en) * 1992-05-08 1993-11-22 Nippon Oil Co Ltd Ethylene/alpha-olefin copolymer
    US5240894A (en) 1992-05-18 1993-08-31 Exxon Chemical Patents Inc. Method for making and using a supported metallocene catalyst system
    DE4217171A1 (en) * 1992-05-23 1993-11-25 Basf Ag Continuous gas phase fluidized bed process for the production of ethylene homopolymers and copolymers
    EP0572034A2 (en) * 1992-05-29 1993-12-01 Idemitsu Kosan Company Limited Ethylenic copolymer and ethylenic copolymer composition
    IT1255514B (en) * 1992-09-24 1995-11-09 Luigi Resconi ETHYLENE COPOLYMERS WITH OLEPHINIC MONOMERS, PROCESS FOR THEIR PREPARATION AND CATALYST
    ES2096346T5 (en) * 1992-11-02 2007-11-01 Exxonmobil Chemical Patents, Inc. MIXTURES OF ETHYLENE COPOLYMERS FOR HOT FUSION ADHESIVES.
    US5464905A (en) * 1992-11-19 1995-11-07 Mitsui Petrochemical Industries, Ltd. Ethylene/α-olefin copolymer composition, graft modified ethylene/α-olefin copolymer composition, ethylene copolymer composition, and multi-stage olefin polymerization process
    EP0601495B1 (en) * 1992-12-07 2002-04-24 Mitsubishi Chemical Corporation Resin composition for extruded forms
    IT1264680B1 (en) * 1993-07-07 1996-10-04 Spherilene Srl SUPPORTED CATALYSTS FOR THE POLYMERIZATION OF OLEFINS
    CN1131953A (en) * 1993-08-06 1996-09-25 埃克森化学专利公司 Polymerization catalysts, their production and use
    IT1271406B (en) * 1993-09-13 1997-05-28 Spherilene Srl PROCEDURE FOR THE PREPARATION OF ETHYLENE POLYMERS AND OBTAINED PRODUCTS
    UA47394C2 (en) * 1995-05-16 2002-07-15 Юнівейшн Текнолоджіз, Ллс Ethylene polymer with improved processability and an article containing the ethylene polymer
    JP3071145B2 (en) * 1995-05-16 2000-07-31 ユニベーション・テクノロジーズ・エルエルシー Production of polyethylene using stereoisomeric metallocene
    FI104826B (en) 1996-01-30 2000-04-14 Borealis As Heteroatom-substituted metallose compounds for catalytic systems in olefin polymerization and process for their preparation
    FI971565A (en) 1997-04-14 1998-10-15 Borealis As Substituted metallocene compounds for catalyst systems intended for polymerization of olefins, intermediates and processes for their preparation

    Patent Citations (1)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    EP0584609A2 (en) * 1992-08-15 1994-03-02 Hoechst Aktiengesellschaft Process for preparing polyolefins

    Non-Patent Citations (1)

    * Cited by examiner, † Cited by third party
    Title
    CHEN Y -X ET AL: "(1,3-Propanediyl) silylene-bis(1-indenyl) dichlorozirconium Synthesis and polymerization catalysis", JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 1, no. 487, 8 February 1995 (1995-02-08), pages 29-34, XP004024264 *

    Also Published As

    Publication number Publication date
    US6664351B1 (en) 2003-12-16
    MX9600690A (en) 1997-08-30
    NO960650L (en) 1996-04-19
    DE69504178D1 (en) 1998-09-24
    ITMI941279A0 (en) 1994-06-20
    DE69520051T2 (en) 2001-07-19
    US6136936A (en) 2000-10-24
    CN1092672C (en) 2002-10-16
    ZA955102B (en) 1996-06-20
    ATE199018T1 (en) 2001-02-15
    CN1131954A (en) 1996-09-25
    FI960741A0 (en) 1996-02-19
    AU689915B2 (en) 1998-04-09
    MY117891A (en) 2004-08-30
    IL114196A (en) 2005-05-17
    PL314425A1 (en) 1996-09-02
    ES2121402T3 (en) 1998-11-16
    BG100411A (en) 1996-07-31
    AU2885695A (en) 1996-01-15
    KR960703950A (en) 1996-08-31
    JP2005097635A (en) 2005-04-14
    DE69520051D1 (en) 2001-03-08
    JPH09502222A (en) 1997-03-04
    WO1995035333A3 (en) 1996-05-02
    NO960650D0 (en) 1996-02-19
    JP3698437B2 (en) 2005-09-21
    IT1270253B (en) 1997-04-29
    CZ290960B6 (en) 2002-11-13
    FI960741A (en) 1996-04-19
    EP0821011A2 (en) 1998-01-28
    IL114196A0 (en) 1995-10-31
    EP0821011B1 (en) 2001-01-31
    EP0742799B1 (en) 1998-08-19
    CA2169841A1 (en) 1995-12-28
    ES2154440T3 (en) 2001-04-01
    DE69504178T2 (en) 1999-03-11
    NZ289111A (en) 1998-05-27
    ATE169939T1 (en) 1998-09-15
    SK34896A3 (en) 1997-03-05
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    BR9506041A (en) 1997-08-05
    RU2155776C2 (en) 2000-09-10
    ITMI941279A1 (en) 1995-12-20
    SK281515B6 (en) 2001-04-09
    WO1995035333A2 (en) 1995-12-28
    EP0742799A1 (en) 1996-11-20
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    PL182374B1 (en) 2001-12-31
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